Method for producing bioresourced propionic acid from glycerol

ABSTRACT

A method for producing bioresourced propionic acid from glycerol. Also, a composition comprising more than 85 mass % of bioresourced propionic acid, and to the use of the propionic acid obtained from the method as a solvent, as a food preservative, for producing herbicide or for preparing vinyl propionate.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. application Ser. No.13/055,263, filed on Jan. 21, 2011, which is a national stageapplication of International Application No. PCT/FR2009/051470, filed onJul. 22, 2009, which claims the benefit of French Application No.0854976, filed on Jul. 22, 2008. The entire contents of each of U.S.application Ser. No. 13/055,263, International Application No.PCT/FR2009/051470, and French Application No. 0854976 are herebyincorporated herein by reference in their entirety.

FIELD

The present invention is targeted at a process for the manufacture ofbioresourced propionic acid from glycerol as starting material, the term“bioresourced acid” indicating that the propionic acid is essentiallyobtained from a carbon source of renewable origin.

BACKGROUND

Propionic acid is a material which can be used as solvent, as foodpreservative or in the herbicide manufacture; propionic acid alsoparticipates in the preparation of vinyl propionate, which is used asmonomer in (co)polymers with, for example, ethylene, vinyl chloride or(meth)acrylic esters.

Processes for the synthesis of propionic acid are known in the art. Forexample, patent application DE 102 25 339 A1 describes a process for thepreparation of propionic acid by catalytic hydrogenation of acrylic acidin the presence of molecular oxygen and of a catalyst of an element fromgroups 8 to 11. Conventionally, acrylic acid is obtained by catalyticgas-phase oxidation of propane, propylene and/or acrolein.

One of the problems posed by the processes for the synthesis ofpropionic acid of the art is that they are carried out starting fromnonrenewable starting materials of fossil (oil) origin, in particularpropane or propylene. In point of fact, resources of these startingmaterials are limited and the extraction of oil requires drilling atincreasingly deep depths and under technical conditions which are alwaysmore difficult, requiring sophisticated equipment and the use ofprocesses which are always more expensive in energy. These constraintshave a direct consequence with regard to the cost of manufacturingpropionic acid.

Furthermore, manufacturers for some years have directed their researchand development studies at “bioresourced” processes of synthesis usingrenewable natural starting materials.

For example, for the manufacture of acrylic acid resulting fromrenewable resources, alternative processes have recently been developedstarting from nonfossil plant starting materials. In particular,processes starting from glycerol (also known as glycerin), resultingfrom the methanolysis of fatty substances, have been developed. Thisglycerol is available in large amounts and can be stored and transportedwithout difficulty.

The methanolysis of vegetable oils or animal fats can be carried outaccording to various well known processes, in particular by usinghomogeneous catalysis, such as sodium hydroxide or sodium methoxide insolution in methanol, or by using heterogeneous catalysis. Reference maybe made, on this subject, to the paper by D. Ballerini et al. inl'Actualité Chimique of November-December 2002.

As regards the conversion of glycerol by the chemical route, mention maybe made of the synthesis of acrylic acid in two stages, namely theproduction of acrolein by dehydration of glycerol, which is described inparticular in U.S. Pat. No. 5,387,720, followed by a “conventional”oxidation of the acrolein to produce acrylic acid.

The first stage in the manufacture of acrylic acid from glycerol resultsin the same intermediate compound as the conventional manufacturingprocess starting from propylene, namely acrolein, according to thereaction:CH₂OH—CHOH—CH₂OH→CH₂═CH—CHO+2H₂Owhich is followed by the second oxidation stage according to thereactionCH₂═CH—CHO+½O₂→CH₂═CH—COOH

Patent applications EP 1 710 227, WO2006/136336 and WO2006/092272describe such processes for the synthesis of acrylic acid from glycerolcomprising the stage of gas-phase dehydration in the presence ofcatalysts consisting of inorganic oxides (mixed or unmixed) based onaluminum, titanium, zirconium, vanadium, and the like, and the stage ofgas-phase oxidation of the acrolein thus synthesized in the presence ofcatalysts based on oxides of iron, molybdenum, copper, and the like,alone or in combination in the form of mixed oxides.

However, one of the problems posed by these processes is that theacrylic acid is not the only product formed and that by-products areformed in large amounts, such as propionic acid and impurities, such aswater, acrylic acid dimers, acetic acid, acrolein, benzaldehyde,furfurals or hydroquinone. It is thus generally necessary to purify theacrylic acid by conventional techniques in order to obtain a moreconcentrated acrylic acid solution.

As the quality of the acrylic acid, that is to say its content ofvarious impurities, plays a large role in the subsequent polymerizationprocesses, manufacturers manufacturing this acrylic acid have been ledto bring into play a whole series of purification stages in order toobtain a “standard” acrylic acid, which is normally referred to asglacial acrylic acid (gAA). This gAA does not meet officially recognizedspecifications having a universal nature but means, for itsmanufacturer, the level of purity to be achieved in order to be able tosuccessfully carry out its subsequent conversions. By way of example,for an acrylic acid resulting from propylene, the reactor outlet streamis subjected to a combination of stages which can differ in theirsequence depending on the process: removal of the noncondensableproducts and of the bulk of the very light compounds, in particular theintermediate acrolein in the synthesis of the acrylic acid (crude AA),dehydration removing the water and the formaldehyde (dehydrated AA),removal of the light products (in particular the acetic acid), theremoval of the heavy products, optionally removal of certain residualimpurities by chemical treatment.

This process is highly analogous to the process for synthesis frompropylene in so far as the intermediate product, the acrolein, resultingfrom the first stage is the same and as the second stage is carried outunder the same operating conditions. However, the first-stage reactionof the process of the invention, dehydration reaction, is different fromthe propylene oxidation reaction of the normal process. The dehydrationreaction, carried out in the gas phase, is carried out using solidcatalysts different from those used for the oxidation of propylene. Theaerolein-rich stream resulting from the first dehydration stage,intended to feed the second stage of oxidation in the acrolein to giveacrylic acid, comprises a greater amount of water and in additionexhibits substantial differences as regards by-products resulting fromthe reaction mechanisms involved being given material formed by thedifferent selectivities in each of the two routes.

In order to illustrate these differences, the data relating to thepresence of various acids in the crude acrylic acid, that is to say inthe liquid phase exiting from the reactor of the second stage accordingto the state of the art, are collated in table 1 below.

TABLE 1 Impurity/AA (crude acrylic acid) ratio by weight Ex-propyleneprocess Ex-glycerol process Acetic acid/AA   <5%  >10% Propionic acid/AA<0.1% >0.5%

Some of the main differences, in terms of constituents of the liquidstream exiting from the oxidation reactor, between the ex-propylene andex-glycerol processes are illustrated in table 1. Naturally, althoughthis is not mentioned in the table, a whole series of oxygen-comprisingcompounds, alcohols, aldehydes, ketones and other acids, the necessaryseparation of which is known to a person skilled in the art, is alsofound in the crude acrylic acid, whether it originates from theex-propylene process or from the ex-glycerol process.

The acetic acid and the propionic acid cause difficulties for theacrylic acid, in particular because they are not converted during thepolymerization process; they are saturated and thus cannot bepolymerized. Depending on the polymerization process involved and theapplications targeted for the polymer, these impurities may remain inthe finished product and risk conferring undesirable corrosiveproperties on the finished product or be reencountered in the liquid orgaseous discharges generated by the polymerization process and causeorganic pollution, which is also undesirable. They therefore have to beremoved.

The acetic acid can be removed by distillation in a light fraction, anoperation generally denoted topping. However, the reduction in theconcentration of acetic acid in the context of the ex-glycerol processresults in a consequent loss of acrylic acid in the light fraction, as aresult, on the one hand, of the large difference existing between itsinitial content in the crude acrylic acid and its targeted content inthe technical acrylic acid and, on the other hand, of the existence ofhydrogen bonds existing between the carboxyl groups of the twomolecules. This disadvantage is important economically as the productionof a glacial acrylic acid with an acetic acid content of less than 0.1%by weight can only be carried out at the expense of the degree ofrecovery of the acrylic acid exiting from the oxidation reactor.

As regards the propionic acid, the extremely small difference involatility existing between this impurity to be removed and the acrylicacid to be purified (of the order of 1° C.) prevents any purification ofthe acrylic acid by distillation under economically acceptableconditions.

There exists, in the known art, no process which makes possible themanufacture of compositions sufficiently concentrated in propionic acidof renewable origin to allow them to be used in the conventionalapplications of the propionic acid obtained with fossil startingmaterials.

DETAILED DESCRIPTION

Advantageously and surprisingly, the Company applying for the presentpatent application has employed a process for the industrial manufactureof propionic acid from glycerol.

The process according to the invention makes it possible to dispense atleast in part with starting materials of fossil origin and to replacethem with renewable starting materials.

The propionic acid obtained according to the process according to theinvention has a quality such that it can be used in all applications inwhich it is known to use propionic acid, including in applications withthe highest standards.

A subject matter of the invention is a process for the manufacture ofbioresourced propionic acid from glycerol comprising the followingstages:

-   -   gas-phase catalytic dehydration of the glycerol to give        acrolein, (I)    -   partial condensation by cooling and extraction of a portion of        the water present in the reaction medium from (1), (1′)    -   gas-phase catalytic oxidation of the acrolein to give acrylic        acid, (2)    -   extraction of the acrylic acid present in the stream from the        oxidation by absorption with a solvent, (3)    -   drying the acrylic acid solution by distillation in the presence        of a water-immiscible solvent, (4)    -   distillation of the solution thus obtained in order to remove        the light compounds (topping), (5)    -   distillation of the heavy fraction resulting from the preceding        stage (5) in order to remove the heavy compounds (tailing), (6)        combined with a stage of extraction of the acrylic acid by        fractional crystallization applied to one of the following        streams: the heavy fraction from (4), heavy fraction from (5) or        light fraction from (6), in order to isolate crystals of        purified acrylic acid and a solution of mother liquors depleted        in acrylic acid    -   catalytic hydrogenation of the mother liquors isolated in the        fractional crystallization stage in the presence of molecular        hydrogen in order to form a propionic acid solution    -   separation of the propionic acid, for example by distillation.

The process according to the invention makes it possible to obtain abioresourced propionic acid obtained from renewable resources.

A renewable starting material is a natural resource, the stock of whichcan be reconstituted over a short period on the human scale. Inparticular, it is necessary for the stock to be able to be renewed asquickly as it is consumed. For example, plant materials exhibit theadvantage of being able to be cultivated without their consumptionresulting in an apparent reduction in natural resources.

Unlike the materials resulting from fossil materials, renewable startingmaterials comprise ¹⁴C. All the samples of carbon drawn from livingorganisms (animals or plants) are in fact a mixture of 3 isotopes: ¹²C(representing approximately 98.892%), ¹³C (approximately 1.108%) and ¹⁴C(traces: 1.2×10⁻¹⁰%). The ¹⁴C/¹²C ratio of living tissues is identicalto that of the atmosphere. In the environment, ¹⁴C exists in twopredominant forms: in the form of carbon dioxide gas (CO₂) and in theorganic form, that is to say in the form of carbon incorporated inorganic molecules.

In a living organism, the ¹⁴C/¹²C ratio is kept constant metabolicallyas the carbon is continually exchanged with the external environment. Asthe proportion of ¹⁴C is constant in the atmosphere, it is the same inthe organism, as long as it is living, since it absorbs this ¹⁴C in thesame way as the surrounding ¹²C. The mean ¹⁴C/¹²C ratio is equal to1.2×10⁻¹².

¹²C is stable, that is to say that the number of ¹²C atoms in a givensample is constant over time. ¹⁴C is radioactive and the number of ¹⁴Catoms in a sample decreases over time (t), its half-life being equal to5730 years.

The ¹⁴C content is substantially constant from the extraction of therenewable starting materials up to the manufacture of the bioresourcedpropionic acid and even up to the end of the use of the objectcomprising propionic acid.

Consequently, the presence of ¹⁴C in a material, this being the casewhatever the amount thereof, gives an indication with regard to theorigin of the molecules constituting it, namely that they originate fromrenewable starting materials and not from fossil materials.

The amount of ¹⁴C in a material can be determined by one of the methodsdescribed in the standard ASTM D6866-06 (Standard Test Methods forDetermining the Biobased Content of Natural Range Materials UsingRadiocarbon and Isotope Ratio Mass Spectrometry Analysis).

This standard comprises three methods for measuring organic carbonresulting from renewable starting materials, known as biobased carbon.The proportions shown for the propionic acid of the invention arepreferably measured according to the mass spectrometry method or theliquid scintillation spectrometry method described in this standard andvery preferably by mass spectrometry.

These measurement methods evaluate the ratio of the ¹⁴C/¹²C isotopes inthe sample and compare it with a ratio of the ¹⁴C/¹²C isotopes in amaterial of biological origin giving the 100% standard, in order tomeasure the percentage of organic carbon in the sample.

Preferably, the propionic acid according to the invention comprises anamount of carbon resulting from renewable starting materials of greaterthan 20% by weight, preferably greater than 40% by weight, with respectto the total weight of carbon of the propionic acid.

In other words, the propionic acid can comprise at least 0.25×10⁻¹⁰% byweight of ¹⁴C and preferably at least 0.5×10⁻¹⁰% by weight of ¹⁴C.

Advantageously, the amount of carbon resulting from renewable startingmaterials is greater than 75% by weight, preferably equal to 100% byweight, with respect to the total weight of carbon of the propionicacid.

According to the process of the invention, the acrylic acid is purifiedby fractional crystallization. During this purification, two streams areobtained: a first stream concentrated in acrylic acid, which can berecovered in value as acrylic acid, and a second stream (mother liquors)poorer in acrylic acid. This second stream cannot be recovered in valueas acrylic acid. According to the process of the invention, this secondstream is hydrogenated to form bioresourced propionic acid. Themanufacturing process according to the invention makes it possible toobtain a purified acrylic acid and to recover in value the second streamand thus delimit the losses of product during the process.

For the implementation of the process, use is generally made of a streamfeeding the reactor of the stage (1) comprising the glycerol and water,with a water/glycerol ratio by weight which can vary within wide limits,for example between 0.04/1 and 9/1 and preferably between 0.7/1 and 3/1.The dehydration reaction, stage (1), which is an equilibrium reactionbut one favored by a high temperature level, is generally carried out inthe gas phase in the reactor in the presence of a catalyst at atemperature ranging from 150° C. to 500° C., preferably of between 250°C. and 350° C., and an absolute pressure of between 1 and 5 bar (1000and 5000 kPa). It can also be carried out in the presence of oxygen orof a gas comprising oxygen, as described in applications WO 06/087083and WO 06/114506.

The glycerol dehydration reaction is generally carried out over solidacid catalysts. The catalysts which are suitable are materials used in agaseous or liquid reaction medium, in a heterogeneous phase, which havea Hammett acidity, denoted H₀, of less than +2. As indicated in U.S.Pat. No. 5,387,720, which refers to the paper by K. Tanabe et al. in“Studies in Surface Science and Catalysis”, Vol. 51, 1989, chap. 1 and2, the Hammett acidity is determined by amine titration using indicatorsor by adsorption of a base in the gas phase.

These catalysts can be chosen from natural or synthetic siliceoussubstances or acidic zeolites; inorganic supports, such as oxides,covered with mono-, di-, tri- or polyacidic inorganic acids; oxides ormixed oxides or heteropolyacids or heteropolyacid salts.

These catalysts can generally consist of a heteropolyacid salt in whichthe protons of said heteropolyacid are exchanged with at least onecation chosen from elements belonging to Groups I to XVI of the PeriodicTable of the Elements, these heteropolyacid salts comprising at leastone element chosen from the group consisting of W, Mo and V.

Mention may particularly be made, among mixed oxides, of those based oniron and on phosphorus and of those based on cesium, phosphorus andtungsten.

The catalysts are chosen in particular from zeolites, Nafion® composites(based on sulfonic acid of fluoropolymers), chlorinated aluminas,phosphotungstic and/or silicotungstic acids and acid salts, and varioussolids of the type comprising metal oxides, such as tantalum oxideTa₂O₅, niobium oxide Nb₂O₅, alumina Al₂O₃, titanium oxide TiO₂, zirconiaZrO₂, tin oxide SnO₂, silica SiO₂ or silicoaluminate SiO₂/Al₂O₃,impregnated with acid functional groups, such as borate BO₃, sulfateSO₄, tungstate WO₃, phosphate PO₄, silicate SiO₂ or molybdate MoO₃functional groups, or a mixture of these compounds.

The preceding catalysts can additionally comprise a promoter, such asAu, Ag, Cu, Pt, Rh, Pd, Ru, Sm, Ce, Yt, Sc, La, Zn, Mg, Fe, Co, Ni ormontmorillonite.

The preferred catalysts are phosphated zirconias, tungstated zirconias,silica zirconias, titanium or tin oxides impregnated with tungstate orphosphotungstate, phosphated aluminas or silicas, heteropolyacids orheteropolyacid salts, iron phosphates and iron phosphates comprising apromoter.

The reaction medium exiting from the dehydration reactor has a highwater content due to the glycerol charge (aqueous solution) and to thereaction itself. An additional stage (1′) of partial condensation of thewater, such as, for example, that described in the patent application WO08/087315 on behalf of the Applicant Company, will make it possible toremove a portion thereof, so as to bring this gas to a compositionsubstantially identical to that of the ex-propylene process, in order tofeed the second stage of oxidation of the acrolein to give acrylic acid.The term “substantially identical composition” is understood to mean inparticular similar concentrations of acrolein, water and oxygen. Thiscondensation stage (1′) can be carried out with cooling to a temperaturewhich makes it possible to obtain, after removal of the condensed phase,a gas stream comprising water and acrolein in a water/acrolein molarratio of 1.5/1 to 7/1. This partial condensation of the water makes itpossible to prevent damage to the catalyst of the 2nd stage of oxidationof the acrolein to give acrylic acid and to avoid, during the subsequentstages, the removal of large amounts of water, which is expensive andwhich risks bringing about losses of acrylic acid. In addition, it makesit possible to remove a portion of the “heavy” impurities formed duringthe dehydration.

The oxidation reaction, stage (2), is carried out in the presence ofmolecular oxygen or of a mixture comprising molecular oxygen at atemperature ranging from 200° C. to 350° C., preferably from 250° C. to320° C., and under a pressure ranging from 1 to 5 bar in the presence ofan oxidation catalyst.

Use is made, as oxidation catalyst, of any type of catalyst well knownto a person skilled in the art for this reaction. Use is generally madeof solids comprising at least one element chosen from the list Mo, V, W,Re, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sn, Te, Sb, Bi, Pt, Pd, Ru and Rh,present in the metallic form or in the oxide, sulfate or phosphate form.Use is made in particular of the formulations comprising Mo and/or Vand/or W and/or Cu and/or Sb and/or Fe as main constituents.

The gas mixture resulting from stage (2) is composed, apart from theacrylic acid:

-   -   of light compounds which are noncondensable under the        temperature and pressure conditions normally employed: nitrogen,        unconverted oxygen, carbon monoxide and carbon dioxide, which        are formed in a small amount by final oxidation,    -   of condensable light compounds: in particular water, generated        by the dehydration reaction or present as diluent, unconverted        acrolein, light aldehydes, such as formaldehyde and        acetaldehyde, formic acid, acetic acid and propionic acid,    -   of heavy compounds: furfuraldehyde, benzaldehyde, maleic acid,        maleic anhydride, 2-butenoic acid, benzoic acid, phenol,        protoanemonin, and the like.

Stage (3) consists of an extraction of the acrylic acid by absorption ina solvent. The solvent can be water or a mixture of heavy hydrophobicsolvents, such as diphenyl and diphenyl ether. This extraction stage isknown to a person skilled in the art and the latter may refer to thefollowing patents: French patent No. 1 588 432, French patent No. 2 146386, German patent No. 4 308 087, European patent No. 0 706 986 andFrench patent No. 2 756 280. This extraction can be carried out withwater by a countercurrentwise absorption. For this, the gas resultingfrom the reactor is introduced at the bottom of an absorption column,where it encounters, countercurrentwise, water introduced at the columntop. Light compounds (mainly acetaldehyde and acrolein) are essentiallyremoved at the top of this absorption column. The water used asabsorbing solvent can be introduced via a source external to the processbut will preferably be composed, partially or completely, by recoveryfrom at least one of the gaseous reaction streams resulting from theinitial reaction stages, for example the water resulting from stages(1′) and (4), namely the water condensed in stage 1′ or the waterrecovered from the azeotropic drying column top stream. The operatingconditions of this absorption stage are as follows: The gaseous reactionmixture is introduced at the column bottom at a temperature between 130°C. and 250° C. The water is introduced at the column top at atemperature of between 10° C. and 60° C. The respective amounts of waterand of gaseous reaction mixture are such that the water/acrylic acidratio by weight is between 1/1 and 1/4. The operation is carried out atatmospheric pressure.

In a preferred alternative embodiment of the process, during a stage(3′), the acrolein present in the liquid fraction resulting from (3) isrecovered by distillation or stripping with a gas. In this alternativeform of the process, the absorption column can be coupled to a columnfor the distillation of the very light compounds, essentially acroleinunconverted on conclusion of reaction, present in a low concentration inthe aqueous acrylic acid solution recovered at the bottom of theabsorption column. This distillation column, which operates under apressure of from 6×10³ to 7×10⁴ Pa, is fed at the top with the bottomstream from the preceding absorption column and makes it possible toremove, at the top, a stream of acrylic acid enriched in acrolein whichis recycled in the lower part of the absorption column (3) for finalremoval at the top of this same column. An aqueous mixture of acrylicacid in water (ratio by weight from 1/1 to 4/1) is thus obtained whichis freed from the bulk of the unconverted acrolein, which aqueousmixture is known as “crude acrylic acid”. The acrolein can also berecovered by stripping with a gas, such as air or an inert gas mixturepreferably comprising oxygen.

This stage is optional but, in its absence, the crude acrylic acid willbe more concentrated in acrolein, which will have to be removed duringthe subsequent topping stage. Furthermore, this stage (3′) makes itpossible to recover and recycle the acrolein to the reaction stage (2)and thus to increase the overall yield of the process.

Stage (4) is a dehydration or drying stage which is carried out in thepresence of a water-immiscible solvent for acrylic acid. Thisdehydration stage can be carried out by liquid/liquid extraction of theacrylic acid in the presence of the solvent, followed by a stage ofseparation of the monomer, acrylic acid, by distillation.

This dehydration stage is described in numerous patents; see, forexample, patent FR 2 119 764, with methyl isobutyl ketone (MIBK) assolvent, or U.S. Pat. No. 3,689,541, with trimethylcyclohexanone assolvent, or by distillation in the presence of a solvent or of mixturesof solvents forming a heterogeneous azeotrope with the water, such asacetates or methyl isobutyl ketone, such as described, for example, inpatent FR 2 554 809, or solvents additionally forming an azeotropicmixture with acetic acid, such as toluene, as described, for example, inthe patent JP 03.181.440.

In the process of the invention, use will preferably be made, for thisdehydration stage, of an azeotropic distillation using a solvent, suchas MIBK. The distillation column, which operates under a pressure offrom 6×10³ to 7×10⁴ Pa, is equipped with a decanter which receives thecolumn top stream after condensation and provides for the separation ofan upper organic phase, essentially consisting of MIBK, which iscompletely recycled as column top reflux, and of an aqueous phasecomprising the water and most of the formaldehyde. The heating power setfor the boiler of the column is adjusted such as to obtain a solventreflux flow rate such that the ratio by weight of solvent returned asreflux to water present in the crude acrylic acid feeding the columncorresponds to the theoretical azeotropic mixture. The stream obtainedat the column bottom, the dehydrated acrylic acid, is essentially devoidof water (generally less than 1% by weight).

In an alternative embodiment, this column can be coupled to a secondcolumn for recovery of the solvent, so as to recover, in the aqueousstream separated by settling at the top of the azeotropic distillationcolumn, the traces of solvent dissolved in the aqueous phase. Thesesmall amounts of solvent, distilled and condensed at the top of thissolvent recovery column, which operates at atmospheric pressure, aresubsequently recycled in the decanter of the preceding column. Theaqueous stream from the bottom of this solvent recovery column isdiscarded.

Stage (5) is a stage of removal of the light compounds, in particularacetic acid and formic acid, by distillation; it is generally known as“topping”. The stream of dehydrated acrylic acid obtained at the bottomof the azeotropic distillation column is conveyed to the middle part ofa distillation column which operates under a top pressure of the orderof 2×10³ to 2×10⁴ Pa. The stream from the column bottom comprisesacrylic acid freed from the bulk of the light compounds. The column topstream, which is rich in acetic acid and formic acid, can optionally beadditionally treated in order to recover, in a second column in series,the small amounts of acrylic acid entrained with the column top stream.

Stage (6) is a stage of separation of the heavy compounds bydistillation. The bottom stream from the preceding topping column isintroduced at the bottom of a distillation column operating under a toppressure of the order of 2×10³ to 2×10⁴ Pa. A stream of purified acrylicacid described as of technical grade is obtained at the top.

The various stages of separating by distillation necessitate, due to thethermodynamic conditions employed, the addition of polymerizationinhibitors to the streams treated in order to prevent the formation ofheavy compounds formed by polymerization of acrylic acid which areharmful to the satisfactory operation of the assembly. Thepolymerization inhibitors generally used for the stages of purificationof the acrylic acid are phenolic products, such as hydroquinone orhydroquinone methyl ether, phenothiazine derivatives, compounds of thefamily of the thiocarbamates, such as copper di(n-butyl)dithiocarbamate,amino derivatives, such as hydroxylamines, hydroxydiphenylamine orderivatives of the family of the phenylenediamines, nitroxidederivatives of 4-hydroxy 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO),such as 4-hydroxy-TEMPO or 4-oxo-TEMPO, or metal salts, such asmanganese acetate. These inhibitors can be used alone or in combinationand are in addition preferably introduced in combination with anoxygen-comprising gas.

These polymerization inhibitors are generally heavy compounds, thevolatility of which is lower than that of acrylic acid. They are removedat the bottom of the columns. On the other hand, their concentration inthe vapor phase inside the distillation columns is low and insufficientto prevent the initiation of polymers. In order to prevent theappearance and the accumulation of polymers, these additives are usuallyintroduced into the liquid streams feeding the devices, but also at thetop and at various points of the columns and devices, so as to providecontinuous and homogeneous reflux of solution rich in polymerizationinhibitors over all the parts of the devices. Generally, they areconveyed in solution in a liquid, for example in acrylic acid or inwater, if the purification stage relates to aqueous streams.

The process of the invention comprises a stage of purification of thebioresourced acrylic acid which is a separation by fractionalcrystallization.

Fractional crystallization is a well-known separation technique. It canbe carried out in various forms, dynamic crystallization, staticcrystallization or suspension crystallization. Mention may be made, onthis subject, of the French patent 77 04510 of 17 Feb. 1977 (BASF) andthe U.S. Pat. No. 5,504,247 (Sulzer) and U.S. Pat. No. 5,831,124 (BASF)and U.S. Pat. No. 6,482,981 (Nippon Shokubai), some of which target thepurification of acrylic acid synthesized by oxidation of propylene.

The most widely used technique is falling film fractionalcrystallization, dynamic crystallization, optionally in combination witha static crystallization in a molten medium.

The falling film crystallization is generally carried out in a tubularexchanger, in practice multitubular, each tube being fed continuously(at the top) with:

-   -   a liquid stream (solution or melt) of the compound to be        purified, acrylic acid (AA) in the process, falling as a film        preferably along the internal wall of the tube, received at the        tube bottom and recycled at the top (closed loop) for the time        necessary for the crystallization of the amount of compound (AA)        decided upon by the operator,    -   a stream of heat-exchange fluid, for example ethylene        glycol/water or methanol/water, falling as a film, preferably        along the external wall of the tube, also recirculated        throughout the crystallization within the tube, which will        contribute the cold or the heat necessary for the operation of        the stages of each of the steps.

The process is a combination of successive steps which each comprisethree stages:

-   -   Crystallization: the temperature of the heat-exchange fluid is        lowered along a negative temperature gradient starting from a        temperature slightly above the crystallization temperature of        the acrylic acid in the medium, of the order of 14° C. Crystals        form as a more or less thick layer at the surface of the tubes.        When approximately 30 to 80% of AA circulated has crystallized,        after draining, the remaining liquid fraction (mother liquors        rich in impurities) is transferred into a receiver.    -   Sweating: the temperature of the heat-exchange fluid is raised        along a positive temperature gradient in order to remove, by        melting, the impurities trapped in the form of inclusions in the        layer of acrylic acid crystals being formed; the latter are        mainly located in the outermost layer which is in contact with        the recirculated stream increasingly rich in impurities. During        the sweating, the first molecules to melt are eutectic mixtures        of impurities and of AA (acrylic acid), the impurities located        in the layer of crystals migrate towards the outer layer, that        is to say that which was in contact with the recirculated        stream. A small portion of this crystal layer is thus melted and        transferred into a receiver, preferably the same receiver as        that of the mother liquors recovered during the crystallization        stage. This sweating stage can be replaced by a washing        technique, which consists in removing impurities present at the        surface by washing with pure AA, preferably introduced at a        temperature slightly higher than the melting point of the AA        layer. However, this technique is a priori less effective.    -   Melting: the temperature of the heat-exchange fluid is rapidly        increased above the melting point of AA (14° C.) and should        preferably remain below a maximum temperature above which it is        possible to fear a polymerization (explosive) of the medium:        this maximum temperature is of the order of 35-40° C. in order        to remain secure in melting the layer of crystals of purified        AA. The purified liquid recovered is placed in a second        receiver.

Starting from the stream to be purified, the combined three stagesdescribed represent a first purification step. The purified liquid can,on conclusion of this first step, be again subjected to a sequence ofthe three stages described in a 2nd purification step (purificationphase). The mother liquors resulting from this 2nd step are purer thanthose from the preceding step and can thus be used as a mixture with afresh charge of AA to be purified in step No. 1. The same operation canbe carried out in a third purification step, it being possible for themother liquors from this third step to be recycled in the charge of the2nd step and the pure product being recovered by melting the crystals.Generally, the mother liquors from the “n” purification step can berecycled by mixing them with the feed stream of the “n-1” purificationstep.

During the purification phases, the polymerization inhibitors present inthe mixtures to be purified are treated as impurities and are thusremoved in the mother liquors. In order to prevent the formation ofpolymer in the molten crystallizate, an inhibitor compatible in natureand concentration with the final use of the monomer is preferably added.This addition will in particular be carried out during the final meltingstage of a step fed with a stream devoid of polymerization inhibitor,such as, for example, the final “n” purification step fed solely with apurified stream from the “n-1” step.

The mother liquors collected subsequent to the first purification stepcan be treated in a “−1” step according to the same three-stage process.The crystallizate recovered can be used as supplement for the feedcharge of the first step. The mother liquors from the “-1” step are thentreated according to the same process for a further separation, thecrystallizate of which will participate as charge in the stepimmediately above and the mother liquors of which are again subjected tothe process in a lower “-2” step. The steps “-1”, “-2”, and the like,constitute the concentration steps (the successive steps make itpossible to concentrate the impurities in the mother liquor streams).Generally, the mother liquors from the “n” concentration steps aretreated according to the same three-stage process in the subsequent“n-1” step. The repetition of these operations (concentration phase)will make it possible to concentrate the impurities in a stream ofmother liquors increasingly rich in impurities, while the fractions ofpure acrylic acid will be returned to the initial step. Thus, it ispossible to recover the acrylic acid entrained in the initial motherliquors in order to improve the recovery yield and furthermore to obtaina mixture “enriched” in impurities and in propionic acid.

The successive concentration steps are characterized by streams ofmother liquors increasingly concentrated in impurities and in propionicacid as these steps accumulate. In doing this, the crystallizationtemperature of these mixtures becomes increasingly low, which has theeffect of increasing the energy cost of cooling. Furthermore, the timenecessary to crystallize the same amount of acrylic acid is increasinglylong, which has the consequence of reducing the productive output of thepurification for the same crystallization surface area. Consequently,the number of the concentration steps will generally preferably behalted before the total concentration of the impurities and of propionicacid in the mother liquors exceeds 50% by weight of the stream.

Depending on the purity of the starting material, the purity of theexpected purified product and the recovery yield desired, the completeprocess for an initial AA quality of “technical” type preferablycomprises from 1 to 5 steps of purification of acrylic acid and from 1to 5 steps for the concentration of the impurities and of the propionicacid, more preferably from 1 to 4 steps of purification and from 1 to 4steps for the concentration of the impurities and of the propionic acid.This is an advantage for the process according to the invention as thesepurification and concentration steps require the consumption of a greatdeal of energy; a limited number of steps makes it possible to obtain amore economical process while obtaining a good yield of propionic acid.

In order to further improve the recovery yield, it is also possible tocarry out the final concentration step in a static crystallizer. In thiscase, the mixture to be crystallized is placed in contact with a cooledwall. It can, for example, be an exchanger composed of metal platesthrough which a heat-exchange fluid circulates and which are immersed ina vessel containing the crystallization mother liquors from thepreceding steps. The AA forms a crystal layer on the walls of the platesand the mother liquors concentrated in propionic acid and in impuritiesare recovered.

During the process according to the invention, at least one stream ofmother liquors, preferably the stream of mother liquors from the finalconcentration step, is isolated.

According to the invention, the stream of mother liquors isolated duringthe fractional crystallization is hydrogenated in the presence ofmolecular hydrogen in order to obtain propionic acid.

The stream of mother liquors preferably comprises from 50 to 90% byweight of acrylic acid.

This hydrogenation can be carried out in the liquid phase or in the gasphase.

For example, the hydrogenation can be carried out:

-   -   by homogeneous liquid-phase catalysis, it being possible for the        catalyst to be a ruthenium-phosphine complex and the solvent        being methanol, at a temperature of approximately 60° C. and at        a pressure of approximately 3 MPa;    -   by heterogeneous gas-phase catalysis over a hydrogenation        catalyst, for example copper/zinc deposited on an aluminum        oxide; the reaction is then carried out in a fixed bed at a        temperature between 250° C. and 350° C. and at a pressure of        between 1 atm and approximately 6 atm;    -   by heterogeneous catalysis over a palladium catalyst applied in        the form of a liquid palladium salt solution absorbed on a        porous support, such as silicic acid or an active charcoal, the        salt subsequently being reduced to form metallic palladium. An        advantage of this process is that it can be carried out under        “mild” conditions, that is to say at temperatures of 20 to        80° C. and hydrogen pressures of 1 to 10 atm, which makes it        possible to limit polymerization reactions of the acrylic acid.

This process is described in detail on pages 2 to 4 of the document FR 2219 927, the content of which is incorporated by reference.

Mention may also be made of the documents Chem. Prum., 37 (1987), pp.651 to 653, and Electroanalytical Chemistry, 60 (1975), pp. 75 to 80,which describe other processes for the hydrogenation of acrylic acid togive propionic acid.

Preferably, the hydrogenation is carried out in the gas phase: accordingto this alternative form, the hydrogenation catalyst is subjected toless interference from the possible presence of polymerizationinhibitors.

In the liquid phase, in the case where a sulfur-comprisingpolymerization inhibitor was used during the preceding stages ofseparation by distillation, it is preferable to carry out, beforehydrogenation, a stage of prior purification of the mother liquors, forexample by distillation, a sulfur-free polymerization inhibitoroptionally being added during this purification. It is also possible touse a “capturing body” before hydrogenation, that is to say to placesolid compounds capable of scavenging sulfur-comprising inhibitors, suchas ZnO, Ti_(x)Ce_(y)O₂, such as described in the application US2009/065400, and/or supported metals, such as Mo and/or Ni and/or Co, inthe oxide or sulfide form, before introducing the hydrogenation catalystor upstream of the latter.

The propionic acid solution resulting from hydrogenation reactioncomprises impurities, such as acetic acid, which can be easily separatedby an additional stage of purification by distillation.

At the end of the process, a bioresourced propionic acid composition isobtained having as object a bioresourced propionic acid compositionhaving a concentration of propionic acid of greater than 85% by weight,preferably of greater than 95% by weight and more preferably of greaterthan 99% by weight.

The invention also relates to the use of said bioresourced propionicacid composition or of the bioresourced propionic acid obtainedaccording to the process of the invention as solvent, as foodpreservative or in herbicide manufacture, in the preparation ofperpropionic acid or in the preparation of vinyl propionate, which isused as monomer in (co)polymers.

The application of a stage of fractional crystallization of the acrylicacid combined with the hydrogenation of the mother liquors isolated atthe end of this stage exhibits the advantage of fully achieving theobjectives desired in the present patent application, that is to say toobtain a bioresourced propionic acid and to limit the losses of productduring the manufacture of a purified acrylic acid using an ex-glycerolprocess.

The process for the manufacture of propionic acid according to theinvention is illustrated by the following examples.

EXAMPLE 1 Manufacture of Crude Acrylic Acid from Glycerol

The preliminary stage consists in purifying the crude glycerol obtainedfrom vegetable oil, the salts being removed. The crude glycerol solutionconsists, by weight, of 89.7% of glycerol, 3.9% of water and 5.1% ofsodium chloride. This stream (6400 g) is continuously conveyed as feedto a stirred 2 liter reactor heated by an external electrical reactorheater. The glycerol and water vapors are condensed in a refluxcondenser and recovered in a receiver. This purification operation iscarried out under a pressure of 670 Pa (5 mmHg). 5710 g of a glycerolsolution devoid of sodium chloride are obtained.

Passing to stage (1) of the process, the reaction for the dehydration ofthe glycerol to give acrolein and the condensation (1′) of a portion ofthe water are carried out. The dehydration reaction is carried out inthe gas phase in a fixed bed reactor in the presence of a solid catalystconsisting of a tungstated zirconia ZrO₂/WO₃ at a temperature of 320°C., at atmospheric pressure. A mixture of glycerol (20% by weight) andwater (80% by weight) is conveyed to an evaporator in the presence ofair in an O₂/glycerol molar ratio of 0.6/1. The gas medium exiting fromthe evaporator at 290° C. is introduced into the reactor, consisting ofa tube with a diameter of 30 mm charged with 390 ml of catalyst andimmersed in a salt bath (KNO₃, NaNO₃ and NaNO₂ eutectic mixture)maintained at a temperature of 320° C.

At the outlet of the reactor, the gaseous reaction mixture is conveyedto the bottom of a condensation column. This column consists of a lowersection filled with Raschig rings surmounted by a condenser in which acold heat-exchange fluid circulates. The cooling temperature in theexchangers is adjusted so as to obtain, at the column top, a temperatureof the vapors of 72° C., at atmospheric pressure. Under theseconditions, the loss of acrolein at the condensation column bottom isless than 5%.

In the following stage (2), the gas mixture is introduced, afteraddition of air (O₂/acrolein molar ratio of 0.8/1) and of nitrogen in anamount necessary in order to obtain an acrolein concentration of 6.5 mol%, as feed of the reactor for the oxidation of acrolein to give acrylicacid. This oxidation reactor consists of a tube with a diameter of 30 mmcharged with 480 ml of a commercial catalyst for the oxidation ofacrolein to give acrylic acid based on mixed oxides of aluminum,molybdenum, silicon, vanadium and copper and immersed in a salt bath,identical to that described above, for its part maintained at atemperature of 345° C. Before introducing over the catalytic bed, thegas mixture is preheated in a tube which is also immersed in the saltbath.

At the outlet of the oxidation reactor, the gas mixture is introduced atthe bottom of an absorption column, stage (3), operating at atmosphericpressure. This column is filled with random packing made of stainlesssteel of ProPak type. In the lower part, over ⅓ of its total height, thecolumn is equipped with a condensation section; a portion of thecondensed mixture recovered at the column bottom is recycled, aftercooling in an external exchanger, at the top of this condensationsection. The upper part of the column is cooled by exchange of heatthrough the wall. The temperature of the vapors at the column top is 25°C. and that of the aqueous solution of crude acrylic acid obtained atthe column bottom is 35° C. The product obtained at the bottom (crudeacrylic acid) comprises 40% of water and a mixture of acrylic acid(predominant product) and of impurities, present in “impurities/AA”ratios by weight shown in table 1 below. An aqueous hydroquinone (HQ)solution is introduced continuously into the recirculation loop at thecolumn bottom at a concentration of 0.1% by weight, with respect to theacrylic acid.

EXAMPLE 2 Purification of the Crude AA Obtained Ex-Glycerol to GiveTechnical AA

The aqueous solution obtained is subjected to a stage (4) of drying bydistillation in order to remove the water in the form of an azeotropicmixture with methyl isobutyl ketone (MIBK). The column, packed withProPak elements representing an efficiency of 15 theoretical plates, isfed at its middle with crude AA and at the top with MIBK in anMIBK/water present in the crude AA ratio by weight of 3/1. A solution ofstabilizers in MIBK is injected continuously at the column top, whichsolution comprises the stabilizers hydroquinone, phenothiazine and butyldibutyldithiocarbamate (respectively: 35 ppm, 70 ppm and 35 ppm, withrespect to the acrylic acid present in the feed stream). The azeotropicmixture distills at a top temperature of 45° C. under a pressure of1.2×10⁴ Pa.

The dehydrated acrylic acid recovered at the column bottom comprises nomore than 0.4% of water.

It is sent, stage (5), as feed of a topping column, which makes itpossible to remove the light compounds, essentially acetic acid, at thetop. This column, packed with ProPak elements (20 theoretical plates) isfed at its middle with the stream of dehydrated AA and a stream rich inacetic acid is distilled at the top under a pressure of 1.3×10⁴ Pa at atop temperature of 77° C. with a reflux ratio of 7/1. A solution ofstabilizers in technical acrylic acid comprising the stabilizershydroquinone and butyl dibutyldithiocarbamate (400 ppm, with respect tothe acrylic acid present in the feed stream) is introduced at thedistillation column top. The yield for recovery of the acrylic acid inthis stage is 97%.

The topped acrylic acid recovered at the bottom of this column has anacetic acid content of 0.07%. It is conveyed, stage (6), as feed of atailing column provided with 17 perforated plates comprising weirs whichmakes it possible to remove the heavy compounds at the bottom. Thiscolumn operates under a pressure of 6.7×10³ Pa with a top temperature of73° C. and with a reflux of 0.5/1. A solution of stabilizers intechnical acrylic acid, comprising the stabilizers phenothiazine andbutyl dibutyldithiocarbamate (400 ppm, with respect to the acrylic acidpresent in the feed stream), is introduced at the top plate of thedistillation column and the condensed distillate stream is additivatedwith a solution of hydroquinone in pure AA (200 ppm, with respect to thedistilled acrylic acid). The acrylic acid obtained at the column topconstitutes the technical acrylic acid (TAA).

The analyses of the technical grade acrylic acid show that the productcomprises 0.07% of acetic acid, 0.66% of propionic acid, 0.11% of maleicanhydride, 0.11% of water, 0.023% of 2-butenoic acid, 0.01% of furfural,0.02% of benzaldehyde, 0.01% of protoanemonin and 0.02% of acrolein.

The yield for recovery of the acrylic acid in this stage is 95.5%.

EXAMPLE 3 Manufacture of Propionic Acid from Ex-Glycerol TechnicalAcrylic Acid Purified by Crystallization (1)

The stream of acrylic acid of technical quality obtained in example 2 issubjected to a series of purification and concentration steps byfractional crystallization, as described in the present application. Thearrangement used is a falling film crystallizer consisting of a verticaltube made of stainless steel filled with heat-exchange fluid (ethyleneglycol/water mixture) circulating in a closed circuit, via a pump,through an external heat exchanger which can be programmed as atemperature gradient (Lauda cryostatic bath). This tube is fed at thetop in the form of a liquid film which flows uniformly over its externalwall. The liquid constituting the mixture to be crystallized, recoveredin a receiving tank at the bottom, recirculates as a loop in a laggedcircuit in order to again feed the tube at the top, via a pump.

The stream of technical acrylic acid is subjected to a series of severalsuccessive purification steps, each step comprising the followingstages:

-   -   Crystallization: the heat-exchange fluid is rapidly cooled, so        as to lower the temperature of the falling film of acrylic acid        down to the temperature of crystallization of the acrylic acid        in the mixture, determined beforehand from a sample of the        mixture to be purified, and then a negative temperature        gradient, of 0.1 to 0.5° C./min, is imposed on the heat-exchange        fluid. When the volume of crystallized acrylic acid, measured by        difference by evaluating the level of liquid in the collecting        container at the bottom of the crystallizer, reaches 70% of the        starting mixture, the recirculation of the falling film of        mixture to be purified is halted and the tube is drained. The        liquid mixture of the mother liquors thus obtained is separated        and stored in a receiver.    -   Sweating: the heat-exchange fluid is reheated, so as to bring        about the melting of a portion (5%) of the layer of crystallized        acrylic acid at the surface of the tube. The mother liquors from        this sweating stage are collected and stored in the same        receiver as the mother liquors from the preceding stage.    -   Melting: the heat-exchange fluid is rapidly reheated up to a        temperature of 30° C., until the crystallized layer has        completely melted. The purified liquid stream is placed in a        different receiver.

The product purified by melting in the final stage of the firstpurification step is conveyed to the second purification step, where itwill be subject to a fresh series of the three purification stages underthe same operating conditions. The mother liquors from the secondpurification step are subsequently mixed with a fresh charge of the feedstream of technical AA in step 1. This process is thus repeated untilthe desired quality is obtained in the molten purified product.

In order to limit the losses of acrylic acid which are concentrated inthe mother liquors from a first purification step, a series ofsuccessive concentration steps, exhibiting the same stages as thepurification steps, is carried out in which the crystallizate from the“n-1” step is conveyed as feed of the “n” step and the mother liquorsfrom this “n-1” step are conveyed as feed of the “n-2” step. These stepsare carried out under the same operating conditions as the purificationsteps, except for the volume of crystallized acrylic acid targeted,before passing from the crystallization stage to the sweating stage,which is 60% of the product fed.

The final crystallization step is carried out in static mode. The streamto be purified is placed in a container made of stainless steel with ajacket through which circulates a cold fluid maintained at thecrystallization temperature of the medium, determined beforehand by ameasurement of crystallization temperature. A vertical tube made ofstainless steel filled with heat-exchange fluid (ethylene glycol/watermixture) circulating in a closed circuit, via a pump, through anexternal heat exchanger which can be programmed as a temperaturegradient is immersed in this container.

In a first stage, the temperature of the heat-exchange fluid in the tubeis rapidly lowered to the crystallization temperature of the medium andthen a negative temperature gradient of 0.1 to 0.5° C./min is imposed.When the crystallized volume reaches approximately 50% of the startingproduct, the mother liquors are removed, a sweating stage is thencarried out and, finally, the melting stage is carried out, as in theupper crystallization steps in dynamic mode.

Applied to the technical acrylic acid obtained from glycerol oncompletion of the purification stages of example 2, a sequence of 4purification steps and 3 concentration steps, including acrystallization step in static mode, made it possible to obtain acrylicacid of “glacial” quality comprising 50 ppm of acetic acid, 410 ppm ofpropionic acid, less than 1 ppm of maleic anhydride, less than 80 ppm ofwater, less than 1 ppm of 2-butenoic acid, less than 1 ppm of furfural,less than 1 ppm of benzaldehyde, less than 1 ppm of protoanemonin andless than 1 ppm of acrolein.

The yield for recovery of AA in this purification stage is 96.5%.

The residual mother liquors from the final concentration step have thefollowing composition:

-   -   Acrylic acid: 82.4% by weight    -   Acetic acid: 1.7% by weight    -   Propionic acid: 7.4% by weight    -   Diacrylic acid: 0.6% by weight    -   Furfurals: 0.3% by weight    -   Benzaldehyde: 0.6% by weight    -   Water: 2.5% by weight    -   Hydroquinone: 0.5% by weight

Manufacture of the Propionic Acid Solution

A jacketed tubular evaporator made of stainless steel (length of thetube 100 cm, internal diameter 2.5 cm, wall thickness 4 mm) was packedover its entire length with Raschig rings made of silica.

A jacketed tubular reactor made of stainless steel identical to theevaporator was packed, from the bottom upwards, first over a length of 5cm with Raschig rings and then the jacketed tubular reactor was packedwith a homogeneous mixture of 130 ml=135.1 g of the Johnson Mattheyhydrogenation catalyst of 50B type (0.3% by weight of Pd on γ-Al₂O₃, as2 mm spheres) and of 226 ml of Raschig rings. The remainder of thelength of the jacketed tubular reactor was packed only with Raschigrings.

The intermediate space both of the jacketed tubular evaporator and ofthe jacketed tubular reactor was provided with an oil forming aheat-exchange fluid which exhibits a temperature of 185° C.

10 g/h of the residual mother liquors were introduced (from the topdownwards) into the jacketed tubular evaporator. 16 mol/h of molecularhydrogen were passed through the tubular evaporator countercurrentwiseto these mother liquors.

The mixture of acrylic acid and of molecular hydrogen exiting from theevaporator was immediately conveyed, from the bottom upwards, throughthe jacketed tubular reactor. The end of the latter is at atmosphericpressure. The temperature in the middle of the reactor is approximately220° C. The unreacted acrylic acid and the propionic acid produced wererecovered by condensation in a separator at 10° C.

After an operating time of 100 h, the condensate comprised 813 g ofpropionic acid.

After distillation, a propionic acid solution having a purity of 99.1%is recovered.

EXAMPLE 4 Manufacture of Propionic Acid from Ex-Glycerol TechnicalAcrylic Acid Purified by Crystallization (2)

The same purification of the ex-glycerol technical AA by crystallizationis carried out as in the preceding example, except that an additionalconcentration step in dynamic mode is carried out, e.g. 4 purificationsteps and 4 concentration steps, including one in static mode.

The yield for recovery of AA in this purification stage is 99.3%.

The mother liquors recovered after the final concentration stage havethe following composition:

-   -   54.4% of acrylic acid,    -   7.3% of water,    -   8.9% of maleic anhydride,    -   4.4% of acetic acid,    -   16.7% of propionic acid,    -   and 1.5% of hydroquinone.

Manufacture of the Propionic Acid Solution

In this instance, the hydrogenation is carried out in the liquid phasewith a Pd/C catalyst.

200 g of solution of the mother liquors, 200 g of propionic acid alreadyrecovered, simulating a process with recycling, and 50 g of JohnsonMatthey catalyst of 87G type are added with magnetic stirring at 60° C.to an autoclave and then the combined mixture is reacted with hydrogenunder an absolute pressure of 7 bar for 2 hours. After reaction, 340 gof propionic acid are recovered.

EXAMPLE 5 Manufacture of Propionic Acid from Ex-Glycerol Topped AcrylicAcid Purified by Crystallization

The same treatment series as in example 3 (with a static crystallizationstep) are applied to the stream obtained at the bottom of the toppingcolumn (stage (5) of example 2).

A series of 4 purification steps and 3 concentration steps, including astatic crystallization step, made it possible to obtain acrylic acid of“glacial” quality comprising less than 50 ppm of acetic acid, 500 ppm ofpropionic acid, less than 1 ppm of maleic anhydride, less than 100 ppmof water, less than 1 ppm of 2-butenoic acid, less than 1 ppm offurfural, less than 1 ppm of benzaldehyde, less than 1 ppm ofprotoanemonin and less than 1 ppm of acrolein.

The residual mother liquors from the final concentration step have thefollowing composition:

-   -   Acrylic acid: 67% by weight    -   Acetic acid: 1.6% by weight    -   Water: 2.3% by weight    -   Maleic anhydride: 9.4% by weight    -   Propionic acid: 7.4% by weight    -   Furfurals: 0.3% by weight, and    -   Hydroquinone: 0.8% by weight.

Manufacture of the Propionic Acid Solution

A jacketed tubular evaporator made of stainless steel (length of tube 85cm, internal diameter 3 cm, wall thickness 4 mm) was packed over itsentire length with Raschig rings (material SiO₂, quartz glass; externaldiameter 3 mm, internal diameter 2 mm, length 3 mm).

A jacketed tubular reactor made of stainless steel (length of the tube120 cm, internal diameter 3 cm, wall thickness 4 mm) was packed over itsentire length with a homogeneous mixture of 400 ml=446 g of the JohnsonMatthey hydrogenation catalyst of 48 type (0.5% by weight of Pd onγ-Al₂O₃, extrudates as 3 mm pellets) and of 400 ml of Raschig rings. Theintermediate space both of the jacketed tubular evaporator and of thejacketed tubular reactor was filled with an oil forming a heat-exchangefluid. The oil forming a heat-exchange fluid of the evaporator had atemperature of 210° C. and that of the reactor had a temperature of 180°C.

10 g/h of the residual mother liquors were introduced (from the topdownwards) into the jacketed tubular evaporator. 50 mol/h of molecularhydrogen were passed through the jacketed tubular evaporatorcountercurrentwise to the acrylic acid.

The mixture of acrylic acid and of molecular hydrogen exiting from theevaporator was immediately conveyed from the bottom upwards through thejacketed tubular reactor positioned above the evaporator. The end of thetube is at atmospheric pressure. The temperature in the middle of thereactor is 186° C. The unreacted acrylic acid present in the gas streamproduced and the propionic acid formed are separated by condensation ina separator at 10° C.

After an operating time of 20 h, 13.2 g of propionic acid are recoveredin the condensate.

The propionic acid produced according to the invention is a bioresourcedacid manufactured from nonfossil natural starting materials.

What is claimed is:
 1. A composition comprising at least 85% of propionic acid obtained from bioresourced materials, wherein the propionic acid comprises at least 0.25×10⁻¹⁰% by weight of ¹⁴C, this amount of ¹⁴C being determined by one of the methods described in the standard ASTM D6866-06; wherein the propionic acid obtained from the bioresourced materials has been subjected to purification, wherein the purification comprises the removal of benzaldehydes, furfurals and/or hydroquinones by hydrogenation of a mother liquor of an acrylic acid crystallization.
 2. The composition of claim 1, comprising at least 95% of propionic acid obtained from bioresourced materials.
 3. The composition of claim 1, comprising at least 99% of propionic acid obtained from bioresourced materials.
 4. The composition of claim 1, wherein the propionic acid comprises at least 0.5×10⁻¹⁰% by weight of ¹⁴C, this amount of ¹⁴C being determined by one of the methods described in the standard ASTM D6866-06.
 5. The composition of claim 2, wherein the propionic acid comprises at least 0.5×10⁻¹⁰% by weight of ¹⁴C, this amount of ¹⁴C being determined by one of the methods described in the standard ASTM D6866-06.
 6. The composition of claim 3, wherein the propionic acid comprises at least 0.5×10⁻¹⁰% by weight of ¹⁴C, this amount of ¹⁴C being determined by one of the methods described in the standard ASTM D6866-06. 